Fluoroalkylene silanes and siloxanes

ABSTRACT

Fluorocompounds of the formula CH=CH2(CH2CH2)nRfCH2OR in which Rf is a perfluoroalkylene radical of no more than 18 carbon atoms and R is a hydrogen atoms or acyl radical. These monomers can be polymerized with a free radical catalyst to give OR THE COMPOUNDS CAN BE REACTED WITH *SiH to give the corresponding substituted silicon atom. The novel silicon containing compounds are useful as elastomers, lubricants, and coating compositions.

United States Patent [151 3,681,418

Pierce et al. [4 1 Aug. 1, 197 2 [54] F LUOROALKYLENE SILANES AND3,529,003 9/1970 Rausch et al. ..260/448.2 B

SILOXANES Primary Examiner--Delbert E. Gantz [72] Inventors. 31 2flslldl fi1 Kl Assistant Examiner-P. F. Shaver Att0rneyRobert F. Fleming, Jr.,Laurence R. Hobey, g nowhcm'ning 1 Midland, Harry D. Dingman and NormanE. Lewis Mic 22 Filed: Nov. 5, 1969 [571 ABSTRACT [21] APPL Na; 874,411Fluorocompounds 0f the formula CH=CH- (CH- CH2)nR CHzOR ll'l WhlCh R, 18a perfluoroalkylene radical of no more than 18 carbon atoms and R is a[52] Cl--260/448'2 260/4482 Rim/488 hydrogen atom or acyl radical. Thesemonomers can [51] I t C] be polymerized with a free radical catalyst togive 11 [58] Field of Search ..260/448.2 B, 448.8 R [56] ReferencesCited (CHQCHQHRICHNR UNITED STATES PATENTS or the compounds can hereached with E 8111 to give the corresponding substituted SlllCOl'latom. The novel 2,966,508 12/1960 Kerschner et B silicon containingcompounds are useful as elastomers, 3,012,006 12/ 1961 Holbrook etal....260/448.2 B X lubricants and Coating compositions. 3,143,5248/1964 Cooper et.al.......260/448.2 B X 3,427,271 2/1969 McKellar..260/448.2 B X 7 Claims, N0 Drawings in which R is a lower alkylradical of no more than six carbon atoms; and n is an integer having avalue of from to 2.

For purposes of this invention R, can be any perfluoroalkylene radicalof no more than 18 carbon R can be any lower alkyl radical, such asmethyl, ethyl, butyl, isopropyl, t-butyl, or hexyl.

Thus, included within the scope of the invention are the following:

These fluoroalkylene compounds are prepared by the reduction of CH CH(CHCH ),,R,COOR' with lithium aluminum hydride to obtain CH Cl-l(Cl-l Cl-l),,R Cl-l Ol-l, which in turn can be esterified by reaction with R'COCl.The precursors to the compounds of the invention are prepared byreacting a omega-bromo-perfluoroester with ethylene and thereafterdehydrohalogenating the resulting compound by reaction with an alkalimetal alkoxide. The precursor and its preparation are described indetail in copending application Ser. No. 598,604, filed Dec. 2, 1966,now US. Pat. No. 3,503,645.

Fluoroolefins are known to react with the reducing agent, causingrearrangement of the double bond. For example, the reaction of CF11 CF:

see Kaufman et al., Journal of Organic Chemistry, 32, 2749, (1967).

The unsaturated products of this invention can be polymerized via thecarbon-carbon double bond to produce polymers of the unit formula (CHZCJH- (oHzcHmmomon in which R, R and n are as defined above.

The polymerization of the monomer can be carried out employing freeradical catalyst, for example, peroxides such as di-t-butyl peroxide,dicumyl peroxide and tertiary alkyl peroxides; azo compounds, forexample, azo-bisbutyronitile; organometallic compounds, such astetraethyl lead; and ionizing radiation, such as high speed electrons orgamma rays. The polymerization is carried out by heating the monomer inthe presence of the catalyst at temperatures of from to C. or aboveuntil the desired degree of polymerization is obtained.

In addition, the unsaturated monomers of the invention can becopolymerized with other monomers having aliphatic carbon-carbonunsaturation. Examples of such monomers are fluorinated olefins, such astetrafluoroethylene, perfluoropropylene and trifluoropropylene,trichloroethylene; acrylic monomers, such as methyl acrylate,methylmethacrylate, acrylic acid and butyl acrylate; vinyl monomers,such as vinylchloride, vinylidene fluoride, vinyl acetate and vinylidenechloride; olefins, such as propylene, butadiene, chlorobutadiene,isoprene, styrene alphamethylstyrene, vinyl toluene and ethylene;unsaturated ethers, such as vinylmethylether, the monoallylether ofethylene glycol and divinyl ether; esters such as dial lylphthalate andallyl acetate; amides, such as acryl amide and methacryl amide andnitriles, such as acrylonitrile and allyl cyanide.

The above copolymers can be prepared by conventional polymerizationtechniques. The amounts of the monomers of the invention in thecopolymeric materials can vary from 0.01 to 99.99 mol percent. Thecopolymers are fluids, resins or elastomers, depending on the specificcomposition and degree of polymerization. The materials find use aslubricants, sealants, fibers, coatings and films. For example, acopolymer containing 98 mole percent propylene units and 2 mole percentunits can be melt spun to form fibers or extruded to form a film.

The fluoroalkylene compounds of the invention are also useful asintermediates in the preparation of organofunctional silicon compounds.The unsaturated compounds can be reacted with Sil-l compounds in thepresence of a platinum catalyst to give SiCl-l CH CH ),,R,CH OR in whichR;, R and n are as defined. When E SiCll-I compounds are utilized asprecursors, they must be reacted with CH2=CH(OH1CH2)::R1CH2OCR' toobtain organosilicones with the ester functionality which in turn can behydrolyzed to give SiCl-l Cl-l CH Cl-l RyC H OH.

Thus included within the scope of the invention are silanes of theformula in which R R, and n are as defined, R" is a hydrogen atom, amonovalent hydrocarbon radical or a monovalent halohydrocarbon radical;X is a hydroxyl group or a hydrolyzable radical and a is an integerhaving a value of from 1 to 3.

The above described silanes can be hydrolyzed or cohydrolyzed with othersilanes of the formula Z SiX by hydrolysis techniques well known in theart to yield siloxane polymers consisting essentially of at least oneunit of the formula RO CHzRKCHgOH hOHgCHzSlO:

in which R R, R", n and a are as defined, any remaining units being ofthe formula Z,SiO in which Z is a hydrogen atom, a hydroxyl group, amonovalent hydrocarbon radical or a monovalent halohydrocarbon radical,and b is an integer having a value of from to 3.

The siloxanes can be homopolymers or they can be copolymers havingvarious functional fluoroalkyl-containing units in combination with SiOZSiO Z SiO and Z SiO units. The same or different X, R" and Zsubstituents can be attached to the same silicon atoms.

R" can be any monovalent hydrocarbon radical such as alkyl radicals suchas methyl, ethyl, propyl, isopropyl, butyl, pentyl, isopentyl,neopentyl, hexyl, octyl, dodecyl, octadecyl, 3-methylheptyl,6-butyloctadecyl, tertiary butyl, myricyl and 2,2-diethylpentyl; alkenylradicals such as, vinyl, allyl, hexenyl, butenyl, 3-octenyl,4,9-octadecadienyl and 4-nonenyl; alkynyl radicals such as propynyl,heptynyl, butynyl, decynyl; alkenynyl radicals such as l-penten-3-ynyl,Z-ethyl-lbuten-3-ynyl; cycloaliphatic radicals such as, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, propylcyclohexyl,2,4-dimethylcyclopentyl, cyclohexenyl, bicyclo[3.l.0][3.2.1.l]--nonenyl, spiro [4.5]decyl, dispiro[4. l .42] l-tridecenyl,decahydronaphthyl, 2,3-dihydroindyl and l,2,3,4- tetrahydronaphthyl;aryl radicals such as phenyl, tolyl, xylyl, 3-ethylphenyl, xenyl,naphthyl, anthracyl, pentacenyl, 3,4-methylethylphenyl, 9,9'-bifluoryland 4-mterphenyl; and aralkyl radicals such as Z-phenyl-octyl,3-methyl-2-(4-isopropylphenyl)heptyl, benzyl, Z-ethyltolyl,2-ethyl-p-cymyl, diphenyh'nethyl, 4,5-diphenylpentyl, 2-phenylethyl and2-phenylpropyl.

R" can also be any monovalent halogenated hydrocarbon group such asaliphatic groups such as chloromethyl, 3-chloropropyl,3,3,3-trichloropropyl, perfluorovinyl, chlorooctadecyl or radicals ofthe formula R Cl-l Cl-l where R; can be any perfiuoroalkyl group such astrifluoromethyl, perfluoroethyl, perfluoroisobutyl, perfluoroheptyl orperfluorooctadecyl; aromatic groups such as dichlorophenyl,tetrabromoxenyl, tetrachlorophenyl, alpha,alpha,alpha-trifluorotolyl oriodonaphthyl; cycloaliphatic groups such as chlorocyclohexyl,bromocyclopentyl or chlorocyclohexenyl and aralkyl groups such aschlorobenzyl, beta- (chlorophenyDethyl or beta-(iodophenyl)ethyl orbeta- (bromophenyl)propyl.

X can be any hydrolyzable group such as halogen atoms such as F, Cl, Bror I; groups of the formula OZ when Z is any hydrocarbon or halogenatedhydrocarbon group such as methyl, ethyl, isopropyl, octadecyl, allyl,hexenyl, cyclohexyl, phenyl, benzyl, beta-phenylethyl, 2-chloroethyl,chlorophenyl, 3,3,3-

trifluoropropyl or bromocyclohexyl; any hydrocarbon ether radical suchas Z-methoxyphenyl, 2-ethoxyisopropyl, 2-butoxyisobutyl, p-methoxyphenylor (Cl-l Cl-l O) CH any acyl radical such as acetyl, propionyl, benzoyl,cyclohexoyl, acrylyl, methacrylyl, stearyl, naphthoyl, trifluoroacetyl,chlorobenzoyl or bromopropionyl; or any N,N-amino radical such asdimethylamino, diethylamino, ethylmethylamino, diphenylamino, ordicyclohexylamino. X can also be any amino radical such as NHg,dimethylamino, diethylamino, methylphenylarnino or dicyclohexylamino;any ketoxime radical of the formula ON CM or ON CM in which M is anymonovalent hydrocarbon or halogenated hydrocarbon radical such as thoseshown for R above and M in any divalent hydrocarbon radical bothvalences of which are attached to the carbon, such as hexylene,pentylene or octylene; ureido groups of the formula N(M)CONM" in which Mis any monovalent hydrocarbon or halohydrocarbon radical such as thoseshown for R" above and M is H or any of the M radicals; carbamate groupsof the formula OOCNMM" in which M is any monovalent hydrocarbon radicalor halogenated hydrocarbon radical as illustrated for R" above and M" isH or a M group, or carboxylic amide radicals of the formula NMC=O(M") inM is any monovalent hydrocarbon radical of halogenated hydrocarbonradical as illustrated for R" above and M" is H or a M radical. X canalso be the sulfate group or sulfate ester groups of the formula OSO(OM) where M is any monovalent hydrocarbon or halogenated hydrocarbonradical as above illustrated for R"; the cyano group; the isocyanategroup; and the phosphate group or phosphate ester groups of the formulaOPO(OM) in which M is any monovalent hydrocarbon of halogenatedhydrocarbon radical as above illustrated for R The term hydrolyzablegroup means any group attached to the silicon which is hydrolyzed bywater at room temperature.

As described above, the Z radicals in the siloxane copolymers can be thehydrogen atom, the hydroxyl group or any of the monovalent hydrocarbonsor halohydrocarbons described with respect to R The siloxanes of theinvention are resins, fluids, or elastomers, depending on the particularsubstituents on the silicon atom and the degree of polymerization. Theresins find utility as coating compositions, the fluids as lubricantsand the elastomers as sealants.

The following examples are illustrative and should not be construed aslimiting the invention which is delineated in the claims.

EXAMPLE 1 Under a nitrogen atmosphere, grams (0.5 mole) of CH CHCF CFCOOC H was added dropwise to stirred mixture of 20 grams (0.53 mole) ofLiAll-L, and 400 milliliters of dry ether. During the addition, thetemperature was maintained at from 0 to 5C. After completion of theaddition, the reaction mixture was heated at reflux temperature for 3.5hours. The excess LiAlH, was decomposed by dropwise addition of about100 milliliters of water. Addition of the water was carried out at from0 to 5C. The reaction mixture was then acidified with dilutehydrochloric acid and poured into about 500 milliliters of ice water.The ether layer was separated and dried. After evaporation of the ether,the reaction mixture was distilled to give 68.5 grams of CH CHCF CF CHOH, having a boiling point of 135C.

The I and H resonance spectra were in agreement with the depictedalcohol structure.

EXAMPLE 2 yield 1 10 grams of CHz CHCFzCFzCHzO CCHg I having a boilingpoint of 62C./18 mm Hg. All spectral properties were in agreement withthe assigned structure.

EXAMPLE 3 When the product of Example 3 is mixed with di-tbutyl peroxideand heated to a temperature in the range of 125l50C., polymers of thefollowing unit structure are obtained:

EXAMPLE 4 When the ester,

cm=onrcmi ocim is copolymerized with CH CH(CH CH (CF CH OH in amounts of50 mol percent of each by heating a mixture of the two with di-t-butylperoxide at 125C; a copolymer of units of the formulas is obtained.

EXAMPLE 5 When equimolar amounts of styrene and CHg CHCHgCHzCFgCHgO (1.?Q3115 are copolymerized by heating a mixture of the monomers at 100C. inthe presence of benzoyl peroxide, a copolymer of units of the formulasgrams (0.63 mole) of EXAMPLE 6 Under a nitrogen atmosphere, 110 grams(0.63 mole) of (3,3,3-trifluoropropyl)methylchlorosilane was addeddropwise to a stirred mixture of 100 grams (0.5 mole) of and 0.3milliliter of a 0.1 molar solution of chloroplatinic acid in isopropylalcohol. During the addition the temperature was maintained at 110C. Thereaction mixture wasrthen heated at reflux temperature for 17 hours.Distillation of the reaction mixture gave 1 18 grams (63 percent yield)of pure having a boiling point of 94C./0.25 mm Hg. and a refractiveindex of 1.3925. The spectral properties of the product were consistentwith the assigned structure.

Upon heating a mixture of cm=oncmomcmoc cm and cnomcmsiciir in thepresence of a catalytic amount of di-t-butyl peroxide at refluxtemperatures for about 16 hours, the above-described product wasobtained.

EXAMPLE 7 Following the procedure described in Example 6, the reactionof with methyldichlorosilane in the of chloroplatinic acid yieldedpresence having a boiling point of 87C./1.25 mm Hg. and a refractiveindex of 1.4145.

This same procedure gave ClsSiCHzCHgOFgCFzCHzO CH3 (boiling point of92C./0.75 mm Hg.) when Cl SiH was reacted with the2,2,3,3-tetrafluoro-3-(vinyl)propyl acetate.

EXAMPLE 8 A solution of 10 grams (0.026 mole) of in 15 milliliters ofmethanol was heated at reflux for 2 hours, after which the methanol andlow boiling materials were removed by fractional distillation. The highboiling product was distilled under vacuum to yield 6.2 grams of EXAMPLE9 The dichloro product of Example 7,

was hydrolyzed in an aqueous sodium bicarbonateether solution at roomtemperature. The hydrolyzate was condensed by the addition oftetramethyl guanidine-acetic anhydride and heating at 125C./l5 mm Hg.for 24 hours to give a viscous fluid polymer of units of the formulawhich can be compounded with a filler, such as silica, to form asealant.

Further modification and variation are within the scope of the inventionwhich relates to fluoroethylene compounds and polymer products.

That which is claimed is: l. Organosilicon compounds of the formula X.$.lCI'I CH2(CH2CH2)1;R CH7O R fills l in which, R, is aperfluoroalkylene radical of no more than 18 carbon atoms,

X is a hydroxyl group or hydrolyzable radical; R is the hydrogen atom ora 3. The compound of claim 1 in which R is a radical.

4. A compound in accordance with claim I of the formula 5. A siloxaneconsisting essentially of at least one unit of the formula in which R isthe hydrogen atom or a radical in which R is a lower alkyl radical of nomore than six carbon atoms;

n is an integer having a value of from 0 to 2,

R" is a hydrogen atom, a monovalent hydrocarbon radical or a monovalenthalohydrocarbon radical; and

a is an integer having a value of from 1 to 3, any remaining units beingof the formula Z SiQ in which 7 Z is a hydrogen atom, a hydroxyl group,a monovalent hydrocarbon radical or a monovalent halohydrocarbonradical; and

b is an integer having a value of from 0 to 3.

6. The siloxane of claim 5 consisting essentially of 7. The siloxane ofclaim 5 consisting essentially of units of the formula

2. The compound of claim 1 in which X is a chlorine atom.
 3. Thecompound of claim 1 in which R is a radical.
 4. A compound in accordancewith claim 1 of the formula
 5. A siloxane consisting essentially of atleast one unit of the formula
 6. The siloxane of claim 5 consistingessentially of
 7. The siloxane of claim 5 consisting essentially ofunits of the formula